Stabilized paraffin wax compositions



April 15, 1952 D. w. YOUNG 2,593,381

STABILIZED PARAFFIN WAX COMPOSITIONS Filed NOV. 30, 1948 EFFEcT OF ISTVRETNE ISOBUTYLENE-RESIN ON IMPROVING TENSILE STRENGTH m LBS. PER SQJNCH 8O TENSILE OF EXPERIMENTAL WAX-OIL BLENDS o.47-REs|N (3.2% RESIN PERCENT OILIN152 E.M.P.T. PARAFFIN BM 20 5mm Patented Apr. 15, 1952 2,593,381 FICE' I STABILIZED PARAFFIN WAX COMPOSITIONS David W. Young, Roselle, N. J assignor to Standard Oil Development Company, a corporation of Delaware Application November 30, 1948, Serial N 0. 62,775

1 Claim.

The present invention relates to stabilized parafiin wax compositions and to methods of preparing them. More specifically, the invention relates to improved compositions comprising a major quantity of paraflin wax having improved qualities of light stability, tensile strength, and the like, imparted by the addition of a minor quantity of a synthetic resin of the alkylene benzene-olefinic copolymer type.

In the U. S. patent to Smyers, No. 2,2743%, there is disclosed broadly a process for copolymerizing an alkylene benzene, such as styrene, for example, with an aliphatic olefin, such as isobutylene. The copolymerization is conducted at low temperatures in the presence of a suitable Friedel-Crafts catalyst, such as aluminum chloride, boron fluoride, or the like. The patent also contains a suggestion that resins of this general type may be blended with oils, waxes, and the like. The present invention is a specific improvement based upon certain newly discovered and unexpected properties which may be imparted to parafiin base waxes which, by reason of excessive oil content, would ordinarily be of relatively little value.

Paraffin waxes are widely used for many purposes, one of the most'important of which is the I coating of paper, cardboard, and the like, for the packaging and preservation of numerous kinds of perishable products, particularly foods, and the like. The paraffin wax compositions used for as much as 0.3 to 0.65% by weight of sweater oil these purposes must meet certain high standards of purity, light stability, tensile strength, imperviousness to moisture, and the like. Where paper, cardboard, or other sheet material is first coated with wax compositions and later is rolled or stacked, the composition of the wax should be such as to resist blocking, that is, the adhesion of separate coated sheets or layers under pres-' These waxes have a melting point which sure.

usually lies between about 115 and 155 -F.', limits 'jof about 120 to 150 1]. usually being preferred.-j.j

In order to meet the foregoing requirements, it

has been considered necessary in the prior art that parafiin waxes of petroleum derivation be quite fully de-oiled. To accomplish the de-oiling, it has beennecessary to practice an operationknown as sweating, wherein the wax is held for a substantial period of time at a temperature, very near but slightly below its melting point. Such sweating permits the oil which is trapped, in the wax to separate if the sweating process is continued for a suincient period of time. It is usually considered necessary that the oil content of paraffin waxes of the grade used. for example, on packaging material for foodstuffs,

manufacture.

crease in cost, the removal of the last 0.2 or 0.3%

by the sweating process proceeding very slowly. This invention is p'articularly'applicable to waxes which have a, final oil content between about 0125 and 0.75%, and especially those which contain 0.3 to 0.65% oil. a

One feature of,- the present invention resides in the discovery that by the addition of a small amount of a copolymer oi the general type referred to above, a higher oil content may: be tolerated in paraffin wax' compositions without sacrificing the qualities required as set forth above and, in fact, with resultant improvement in the composition. By incorporating a small quantity of an alkylene benzene-olefin copolynier,

'for example, a copolymer of styrene and isobu tylene containing 40 to -70% by weight of the aromatic constituent and 60 to 30% of the olefin, the light stability, resistance to blocking, tensile strength, and resistance to penetration of moisture vapor are better in aparafiin wax containing than untreated paraflin waxes of the prior art containing a much smaller quantity of sweater It will -be apparentirom the foregoing that one object of thepresent invention is to improve paraffin wax compositions in their light stability characteristics, tensile strength, resistance to blocking, and impermeability to moisture, while at the same time effecting economies in their By this invention, an improved product "is made available at a reduced cost of manufactureevenwhen the unit cost of the added copolymer' is considerably higher than the unit cost of the parafiin. The economies effected in be limited to an over-all content of not more paraflin is a slow and therefore expensive proc-.

production more'than offset the added costs of the polymer which is incorporated in the wax composition. j 'j In general, the quantities of polymer to be addedfare preferably between 0.1 and 1% but may be as much as 2.5% or-even 5% by weight, based on'the total composition. A preferred specific range for wax compositions used for coating wrapping paper, cartons], andvthe like, includes 0.2 to 0.4% of a copolymer which has an aromatic content of 50 to, by Weight. Specifically, a resin produced by copolymerizing styrene and isobutylene by the low temperature process using 50 to 60% by weight of styrene and 40 to 50% of isobutylene isfpreferred for waxes which contain about 0.3 orOA-to 0.65% by weight of sweater oil. In general, the oil content should not be higher than about 0.65% because the rigid specifications required for wax coating compounds and the like, cannot be met even when sunlight and ultra violet light.

3 the copolymer is used, if the wax has such a high oil content. In some cases, oil content as high as 0.75% maybe tolerated but the lower limit of 0.65% is usually applicable.

The particular copolymer used may be varied somewhat. In general, it should have a molecular weight within the range of 2,000 to 40,000 as determined by the Staudinger method. While styrene and isobutylene are specifically preferred as the ingredients of the copolymer, other related compositions may be employed. The alkylene benzenes having from 2 to 4 carbon atoms in the alkylene group and having at least one unsaturated bond in such group may be used and the olefin may be anystraight or branched chain monoolefin of 3 to '8 carbon atoms. Thus, propylene, butylene, amylene, h-exylene, heptylene, and octene or diisobuty'lene are all useful in the copolymerization process.

The methods by which the .copolymers which are used in this invention are produced form no .partof the present invention, being well-known in the prior art. The preferred copolymers, specifically those having a styrene content of 50 to 60% by weight, are odorless, tasteless, granular solids in form, and are especially stable to The physical properties of two samples of such copolymer, commonly designated as S-Polymer, are indicated in the following table:

lntrinsic viscosity is determined by the Flory method. as is well-known in the art.

In preparing blends of parafiin wax and "S- Polymer," the resinous polymers can be added directly to the wax in the desired concentration or they may be blended with a smaller quantity of wax to form a concentrated wax-resin composition which may be added subsequently to the base wax. polymer and wax containing equal parts of each may be prepared in kneaders and subsequently dispersed readily in melted paraflin wax.

Alternatively, high speed agitating equipment may be used to disperse the polymer in the wax either for the preparation of concentrates or for preparing compounds as they are to be sold and used. Unless such dispersing equipment is especially efficient the wax-polymer mixture should be heated to a rather high temperature, for example, 140 C. where it is desired to disperse large quantities, such as 20 to by weight of the polymer in the Wax. However, the addition of smaller amounts of polymer, for example, 0.1 to 5% of the total composition, may be accomplished with mild agitation at temperatures as low as 710 to 75 C. Quantities of the latter order are adequate for purposes of the present invention except where it is desired to make concentrated wax solutions of the polymer, as for subsequent addition to untreated wax.

Example I Standard parafl'in waxes were used as basic materials to which varying quantities of S- Polymers, as described above, having either 50 or styrene content, were added. The specifications of the various waxes are indicated in the following:

Wax Sample No. A B C Grade, ASTM M. P. F. 130/132 140/142 146/145 Oil Content, Per Cent Max 0.32 0. 0. 2 National Formulary Acid Test Max 5 .5 5 Saybolt Color, Min 30 30 30 TABLE II [Physical properties of S-polymers in paraflin Waxes] ASTM D Tensile Penctra- Viscosity Per Cent S P01ymr wax 127-30 H4 tion ASTM R. I. at at 210 F Color S-Polymcr Melting j Il'mh D5-25 C. Oenti- Saybolt Pointflls". 77 F. stokes S-50 A 132. 5 70 11 1. 4316 3. Turbid. 5-50 -A 133 72 13 Not Det. Not Det Do. S50 A 132 73 11 1. 4318 4. 22 Do. 8-50 .A 133 94 11 1.4351 8.00 D0. 850 A 141 5 99 11 1. 4312 16. 12 Do. 8 60 A 132. 5 95 11 1. 4340 6. 44 Do. S-60 A 133 r 99 11 1.4356 11.22 Do. B 142 40 10 1. 4353 4.15 +20 S-5O B 141. 5 96 11 Not Det. 5.01 Turbid. S-50 B 141 97 11 1. 4352 5. 61 Do. 850 B 142 99 11 1. 4355 9. 13 Do. S50 B 141.6 101 10 1. 4378 17. 94 D0. S-60 B 141. 5 104 10 1. 4350 4. 63 Do. 860 B 142 104 11 1. 4347 5. 212 Do. S-60 B 141. 5 105 ll 1. 4356 7.06 Do. 8-60 B 141. 5 113 10 1. 4360 11.47 D0. O 146 55 10 1, 4340 4. 39

8-50 C 146 1 92 9 1. 4350 5. 26 Turbid 8-50 0 146 86 10 l. 4360 0. 00 Do. S-50 C 147 86 9 l. 4359 9. 25 Do. S-50 C 147 97 10 1.4376 18.06 Do. S-60 0 146 82 10 Not Det. Not Det. Not Det S-60 G 146 98 9 Not Det Not Det Not Det S-60 C 146 10 Not Det Not Det Not Det S-60 .C 146 112 9 Not Det Not Det Not Det 1 Results obtained on s constant rate of loading machine.

For example, blends of the A The results in Table II show that tensile strength was increased appreciably by the use of the polymers in each of the three-"types of 'wax. The results show also that the S50 polymer, which had a molecular weight-of about 50,000, increased the viscosity of thewax to a greater extent than the 8-60 polymer which had -a lower molecular weight of 38,000. Inthe proportions used, neither polymer altered' the melting point appreciably and the penetration characteristics remained approximately constant. The refractive index, as determined at "70 C., showed a slight increase as the amount of polymer was increased in the blends. Where the viscosity of the mixture is raised appreciably, slightly higher melting temperatures will probably be required for applying coatings to paper and the like. Although the waxes became turbid, their colors and appearances were not'objectionable in any case.

The proportions of Table II appeared to be mechanically stable, no separation of polymer having been noted. 1 1

Example I I wax having a melting point of about 130 F.

(Type A, above) were prepared as'shown in Table III.

TABLE III 7 Sample No. l l 2 3 4 j 5 7 1' Paraffin (M. P. 130 F.) 100 95 90 '80 l 95 90 -so s-so 1o 20 s-ao 10 2o Viscosity in Centipoise 140F.(60O. 1 19 nr 870 14. 31 2121* a 16 ass 12 25 110 5 1a 45. 590 10 21 145 4 .11 37 .518 s 18 125 3 9 31 465 7 16 11s 2 7 27 42s I 5 14 so 2 5 1" sea 4 13 72 Wax brickcttc type tensile specimens were prepared, and were pulled apart at the rate of 10 inches-per min. on Scott Tester Tensile (lbs. per sq. inch) 136, 288, 330, 3-50, 315, 360, 105.

It will be noted in Table III that over a temperature range-from 140 to 260. F. (about 60 to 127 0.), the styrene-isobutylene copolymers increased the viscosity of par'affln, the 8-50 .polymer of higher molecular weight increasing "viscosity to a greater extent than the S-60 poly' mer..

The tensile strength values of the'resulting compositions as determined on 2. Scott testershow an increase in the higher concentrations as well as in the lower concentrationscf, Table II.

plied by a constant, indicated thegrams of moisture vapor which passed through each sample in 24 hours at 100 F. at 95% relative humidity. As indicated in the following table, moisture penetration was greatly improved where the copolymer was used.

E59 20. pounds ,per quarter square inch. This intent of the paraflin wax.

considered as the temperature in degrees Fahrenheit at which waxed sheets of glassine paper TABLE IV Sample No. l 1 3 4 6 7 1 l Paraffin (M. P. l30 1C), Parts 100 90 I 80 5-50, Parts.w 10 20 I $41!), Parts. "l 10 20 [increased Sp me penetration:

8 1b. coating on :10 lb./ream white sulfite paper 6. 42 0.72 1.15 0.58 1.10 16 lbs. coating on 30 ll)./ream white sulfitc paper 3. 04 0.31 1 34 0.28 0. 49 Greased Specimens, creased four ways under 13 lb. wt... Lhen unfolded for testing 8 lb. coating on 30 lb./rcam white sulflte paper 7.63 1. 47 3. 22 1.81 1.35

16 lbs. coating on 30 lb./ream white sulfite paper 4. 36 0.92 2.26 0.98 0.82

93% relative humidity.

In still other tests it was found that polymers of the general type used in the above examples, in concentrations ranging between 0.3 and 2.5% by weight, did not change the ASTM melting point nor the penetration value at 77 F. of the wax composition. The refractive index at 70 0. increased from 1.4306 to 1.4373 with 0.5% of the 5-50 resin of Examples I and II. Upon further addition of this resin the refractive index dropped to 1.4355 with 2.5% polymer. The tensile strength of the original wax in this test was creased to 40 pounds when 0.5% of the 8-50 resin was added and showed a still further increase asthe amount .of the polymer was increased.

The tendency of sheets of waxed paper to stick together, known as blocking, became greater or a decrease in the degree of refining. The last mentioned feature is a function of the oil con- The block point was began to adhere to each other after being under .pressure of 1.5 pounds per square inch for twenty-four hours. The block points of a parafin wax, of type A, Table II, having a melting point of about 132 F. are shown in Table V.

Comparative values, using a polyethylene modifier in the wax, are also shown.

TABLE V Wt. of Type of Additive Additive, Block Point Per cent F 0. 0 118 F l. 8 119 F 3.0 120 F. 200 Did not block at 120 F. Polyethylene (DXL-7) 0.9 119 F. ,Polyethylene (DXL-7) 1.8 120 F.

Polyethylene (DXL7). 3. 0 Did not block r at 120 F. Polyethylene (DXIFT) 20.0 Did not block at 120 F.

' The paper in each instance was coated with 6 pounds of wax per ream.

The tendency of many paraffin waxes to darken after continued exposure to light is highly ob- :jectiona'ble, particularly in the food packaging industries. Waxes which otherwise meet specifications fully are frequently rejected because of this tendency to become discolored. The light stability of paraflin waxes appears to be materially improved by the use of small quantities of the copolymers described above, the effect being due apparently to the fact that the aromatic nucleus interferes in some way with the normal actinic activity of ultra violet and other light be produced containing 0.6 or even 0.65% by weight of;oi1. When oil content'of these ranges can be tolerated, the production from a sweater unit can be increased very substantially and in some cases it may be doubled. This results in very substantial economy in processing. A com .parison of the physical properties of various portions of .a paraifin wax of the general type of Sample A, Table 11, having various oil and resin contents'is-shown in Table VI.

The improvement of tensile strength effected TABLE VI Peroqlcnt PIoal t 1 er en rg can: g gg X lift? 53.20; p-g 3.50;? 50 ure rav 1 O aining x. a J.

. Sweater violet so. lnch tron 210 F.

Oil) 1 Light Test 3 O. 3 13 4 61 12 1.4330 3. 60 1346 1 0. 2 0. 5 132 50 13 Not Det Not Deli. l Ms 1 0.4 O. 7 132 37 Not Det. Not Det. Not Dot. 1% 3 0 0.3 132 72 l1 7 1.4316 3. 90 91's 1 0 0. 3 132 73 ].l 1. 4318 4. 22 M l 0.1 0. 4 132 08 11 1.4317 3.19 is 1 0. l 0. 4 132 T3 11 1. 4320 4. 19 H" l 0. 2 0.5 132. 5 02 ll 1. 432l 3. 93 it 1 0.2 0.5 132. 5 T2 11 1.4319 4. 23 Ma 1 0. 3 0. 6 133 4!) 12 1. 4319 3. 9l 3. 3" 1 0. 3' 0. 6 132 64 12 l. 4318 4. 22 tic l 0. 4 0. .7 132 47 12 1.4320 3. 89 is 3 0. 4 0. 7 132 53 11 l. 4322 4. 12 It 2 I Sweater oil from 140 F. melting point paraffin wax. Melting point of original sweater oil was 97 However, in this work the original sweater 011 was extracted at F. with methyl ethyl ketone to remove the pure oil fractions from the was removed from the oil on a several samples. The original 140 been given an acid treatment.

2 Oil Staining test at 50 C. for 24 hrs. 3 Heat stability 'test-l=good, 2=fair. 3=I J0f as evaluated by odor and taste.

half was left unwrapped, both being exposed to direct sunlight through the south windows of a laboratory. After a period of 14 days, the samples were observed for color changes. The wax which contained no polymer, being identical with Sample A of Table II above, yellowed considerably in the exposed portion.- The same wax containing quantities from 0.4 to as much as 20% by weight of either the 5-50 or 8-60 resin mentioned above showed no change either in color low melting point wax fractions. After the extraction step, all the M. E. K. hot plate, under slight vacuum. The pure yellow oil was then blended in the M. P. paraffin that was used in the plant to obtain this sweater oil had by the use of small amounts of resin in waxes of various oil content i shown in Figure I of the drawing. Tensile strength specifications commonly require the reduction of oil content to a low level even where the other characteristics mentioned previously are not required. By the addition of small quantities of polymer, a higher oil content can be tolerated and the cost of the added resin usually is substantially less than the cost of further sweating to a very low oil content,

'effecting a considerable over-all economy.

possible to tolerate a considerably higher'final oil content in the finished wax. In one typical refinery operation, wax is charged to sweaters other words, the productivity of a given sweating installation is almost doubled where the final oil content is 0.4% instead of 0.2%.

with the improvements effected by addition of the polymer resin, a satisfactory grade of waxcan In practice, 1 a

80 :weight ofa styrene isobutylene copolymer of 50 to styrene content at a temperature above It will be understood from the foregoing that the wax compositions of the present invention may contain-various other ingredients, such as coloring materials, tackiness agents, and the like, as may be required for specific purposes. Conventional oxidation inhibitors may also be used.

What is claimed is:

The process for producing a wax composition having the properties of wax containing less than 0.3% by weight of oil from wax containing more than 0.3% but less than 0.65% by weight of oil, by incorporating into said wax 0.2 to 0.4% by the melting point of the parafiin wax with mechanical agitation.

DAVID W. YOUNG.

REFERENCES CITED The following references are of record in the {file of this patent:

. fThe S-jPolymers." Rubber Age article; pages 187-190. November 1947. 

